Abstract Water-related problems are increasing globally, and new, low-cost technologies are needed to resolve them. Lignocellulosic waste materials contain reactive functional groups that can be used to provide a bio-based platform for the production of water treatment chemicals. Research on bio-based ion exchange materials in the treatment of real wastewaters is needed. In this thesis, anion exchange materials were prepared through chemical modification (epichlorohydrin, ethylenediamine and triethylamine) using five Finnish lignocellulosic materials as bio-based platforms. Scots pine sawdust and bark (Pinus sylvestris), Norway spruce bark (Picea abies), birch bark (Betula pendula/pubescens) and peat were chosen due to their local availability and abundance. The focus was placed on NO3- removal, but uptake of heavy metals, such as nickel, was also observed and studied. Studies on maximum sorption capacity, mechanism, kinetics, and the effects of temperature, pH and co-existing anions were used to elucidate the sorption behaviour of the prepared materials in batch and column tests. All five materials removed over 70% of NO3- at pH 3–10 (initial conc. 30 mg N/l). Quaternized pine sawdust worked best (max. capacity 32.8 mg NO3-N/g), and also in a wide temperature range (5–70°C). Column studies on quaternized pine sawdust using mining wastewater and industrial wastewater from a chemical plant provided information about the regeneration of exhausted material and its suitability for industrial applications. Uptake of Ni, V, Co and U was observed. Column studies proved the easy regeneration and reusability of the material. For comparison, pine sawdust was also modified using N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride and utilized to remove NO3- from groundwater and industrial wastewater. A maximum sorption capacity of 15.3 mg NO3-N/g was achieved for the synthetic solution. Overall, this thesis provides valuable information about bio-based anion exchange materials and their use in real waters and industrial applications. / Tiivistelmä Edullisia ja kestäviä vedenkäsittelytekniikoita tarvitaan kasvavien vesiongelmien ratkaisemiseen. Lignoselluloosaa, kuten sahanpurua, syntyy suuria määriä teollisuuden sivutuotteena. Sen reaktiivisia funktionaalisia ryhmiä voidaan modifioida kemiallisesti ja valmistaa siten biopohjaisia vedenkäsittelykemikaaleja. Tutkimustietoa oikeiden jätevesien puhdistuksesta biopohjaisilla ioninvaihtomateriaaleilla tarvitaan lisää, jotta materiaalien käyttöä voidaan kehittää ja edistää. Tässä väitöstyössä valmistettiin anioninvaihtomateriaaleja modifioimalla kemiallisesti viittä suomalaista lignoselluloosamateriaalia: männyn sahanpurua ja kuorta (Pinus sylvestris), kuusen kuorta (Picea abies), koivun kuorta (Betula pendula/pubescens) ja turvetta. Menetelmässä käytettiin epikloorihydriiniä, etyleenidiamiinia ja trietyyliamiinia orgaanisessa liuotinfaasissa. Työssä keskityttiin erityisesti nitraatin poistoon sekä synteettisistä että oikeista jätevesistä. Materiaalien soveltuvuutta teollisiin sovelluksiin arvioitiin maksimisorptiokapasiteetin, sorptioisotermien, kinetiikka- ja kolonnikokeiden sekä pH:n, lämpötilan ja muiden anionien vaikutusta tutkivien kokeiden avulla. Kaikki viisi kationisoitua tuotetta poistivat yli 70 % nitraatista laajalla pH-alueella (3–10). Kationisoitu männyn sahanpuru osoittautui parhaaksi materiaaliksi (32,8 mg NO3-N/g), ja se toimi laajalla lämpötila-alueella (5–70°C). Kolonnikokeet osoittivat sen olevan helposti regeneroitavissa ja uudelleenkäytettävissä. Tuotetta testattiin myös kaivos- ja kemiantehtaan jäteveden käsittelyyn, ja kokeissa havaittiin hyviä nikkeli-, uraani-, vanadiini- ja kobolttireduktioita. Männyn sahanpurua modifioitiin vertailun vuoksi myös kationisella monomeerilla, N-(3-kloro-2-hydroksipropyyli)trimetyyliammoniumkloridilla. Tuotteen maksimisorptiokapasiteetiksi saatiin 15,3 mg NO3-N/g ja se poisti nitraattia saastuneesta pohjavedestä. Kokonaisuudessaan väitöskirjatyö tarjoaa uutta tietoa biopohjaisten ioninvaihtomateriaalien valmistamisesta ja niiden soveltuvuudesta oikeiden teollisuusjätevesien käsittelyyn.

[pt] Embora o papel do vanádio no organismo ainda não tenha sido bem definido, sabemos que ele inibe a atividade das ATPases em eritrócitos e células tubulares renais, afetando a função diurética dos rins, o metabolismo de leucócitos e macrófagos, a função do músculo cardíaco, causando efeitos insulina-like em doses farmacológicas. O vanádio é de grande importância para a indústria, é utilizado como catalisador, na produção de vidros e aço. Os trabalhadores em usinas de produção de aço e indústrias que utilizam combustíveis fósseis como fonte de energia, são expostos a quantidades significativas de vanádio, sendo importante o monitoramento dos seus níveis. No presente trabalho foi desenvolvido um método simples e direto para determinação de vanádio em soro usando a espectrometria de absorção atômica em forno de grafite, otimizado por um planejamento composto central. As temperaturas de pirólise e atomização foram de 1240 e 2600 oC, e calibração externa pode ser realizada com soluções de calibração preparadas em HNO3 2,5 % v/v, mostrando-se linear até, pelo menos, 3 ug L(-1). O pré-tratamento da amostra consistiu tão somente de uma diluição (2+1) no mesmo meio, e os limites de detecção e quantificação encontrados foram, respectivamente, 0,3 e 1,0 ug L(-1). A velocidade analítica foi de 8 amostras h-1, para análises em triplicata. Nos estudos de recuperação foram obtidas valores médios de 97,2%; 99,2% e 105,3%, para concentrações de 1, 2 e 3 ug.L(-1), respectivamente. Houve excelente concordância entre os valores encontrados e o certificado na análise de um material de referência certificado. Nos estudos da repetitividade, o maior coeficiente de variação encontrado foi 10,3% na amostra adicionada de 1 ug L(-1). Nos estudos da precisão intermediária, o maior coeficiente de variação foi 5,6% na amostra adicionada de 2 ug L(-1). As incertezas combinadas obtidas foram 1,65x10-1; 2,72x10-1 e 3,72x10-1, para concentrações de 1, 2 e 3 ug L(-1), respectivamente. O tempo de vida do tubo de grafite nas condições otimizadas foi de, aproximadamente, 150 ciclos. O método foi considerado adequado para a determinação rotineira de vanádio em soro em laboratórios clínicos. / [en] Although the role of vanadium in the body has not been yet well defined, it is known that it inhibits the ATPase activity in erythrocytes and renal tubular cells, affecting the diuretic function of the kidneys, the metabolism of leukocytes and macrophages, the function of the heart muscle and causes insulin-like effects in pharmacological doses. Vanadium is of great importance to the industry, and is mostly used as catalyst, and in the production of glass and steel. Workers of the steel industries as well as those in plants that use large amounts of fossil fuels are potentially exposed to large amounts of vanadium, and it is important to monitor their serum levels. In the present study it was developed a simple and direct method for determination of vanadium in serum using graphite furnace atomic absortion spectrometry optimized by a central composite design. External calibration was possible, using calibration solutions prepared in 2 % v/v HNO3. The sample was 2+1 diluted in the same medium and the calibration curve was found linear up to at least 3 ug L(-1). The limits of detection and quantification were respectively 0.3 and 1.0 ug L(-1), in the original sample. Average recoveries were 97.2%, 99.2% and 105.3% for concentrations of 1, 2 and 3 ug L(-1), respectively. Excellent agreement was found between found and certified values in the analysis of a certified reference material. The sample throughput was 8 h-1 (n=3). In the study of repeatability, the largest coefficient of variation was 10.3% in the sample spiked with 1 ug L(-1) of vanadium. In the study of the intermediate precision the higher coefficient of variation was 5.6% in the sample spiked with 2 μg.L-1. The combined uncertainties obtained were 1.65x10-1, 2.72x10-1 and 3.72x10-1, for concentrations of 1, 2 and 3 ug L(-1), respectively. The graphite tube life time in the optimized conditions was 150 cycles, approximately. The method was considered adequate to the routine determination of vanadium in serum in clinical laboratories.

Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.

No description available.

Orientadores: Paulo Roberto Mei , Amilton Sinatora / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-26T20:19:05Z (GMT). No. of bitstreams: 1 Fonseca_SolangeTamarada_D.pdf: 21576321 bytes, checksum: ed8a1cccc8774fff4540b331b49b44b8 (MD5) Previous issue date: 2015 / Resumo: Uma das maneiras de se reduzir os custos no transporte de cargas é aumentando a quantidade de carga transportada por vagão, isto eleva a tensão no eixo do vagão e, consequentemente, a roda deve possuir maior dureza sem perda da tenacidade para suportar o desgaste. Para atingir os níveis de dureza necessários estão sendo desenvolvidas rodas ferroviárias com aços microligados que são definidos como aços carbono-manganês contendo pequenos teores (menores que 0,5% em massa) de elementos de liga, que são fortes formadores de carbonetos como o nióbio (Nb), vanádio (V), molibdênio (Mo) e titânio. Em 2008, a MWL do Brasil iniciou o desenvolvimento de rodas ferroviárias fabricadas com aços microligados, e a partir de 2012, com a colaboração da EPUSP foi necessário o desenvolvimento de uma máquina de ensaio de desgaste tipo disco contra disco que atendesse as especificações da norma AAR (Association of American Railroads). Além disso, havia interesse em se conhecer o comportamento desses aços, sendo assim, seria necessário obter as curvas de resfriamento contínuo (CRC) dos mesmos. A análise destas mostrou que a adição dos elementos microligantes refinou o grão austenítico por formação de finos carbonetos de Nb e V, retardou a formação de ferrita e perlita, o que reduziu o espaçamento interlamelar da perlita; e elevou a temperabilidade dos aços. Entretanto, a adição de microligantes não alterou as temperaturas de início de formação de martensita, mas melhorou a temperabilidade. A formação de martensita não foi finalizada até a temperatura ambiente e todos os aços apresentaram austenita retida junto com a martensita. A análise de corpos de prova retirados das pistas de rolamento das rodas ferroviárias prontas para uso, com estrutura ferrítica-perlítica, revelou que o aço ao V apresentou os melhores resultados em todos os ensaios (tração na temperatura ambiente e 540 ºC, energia absorvida no ensaio Charpy e KIC) quando comparado ao aço sem microligantes ou com a adição de Nb+Mo. O melhor desempenho do aço ao V foi atribuído ao seu menor tamanho de grão austenítico e espaçamento interlamelar da perlita mais refinado. No ensaio de desgaste por deslizamento, a perda de massa foi maior no aço Nb. O primeiro protótipo construído da máquina de desgaste tipo disco contra disco forneceu resultados confiáveis até 250.000 ciclos, não atingindo o valor minímo especificado pela AAR. Entretanto a experiência adquirida foi essencial para projetar um novo protótipo que está em comissionamento / Abstract: One of the main strategies to reduce cost in load transportation is through the increase of the load transported a railroad car. This increase of tension in the wagons axes, require wheels with higher hardness but without loss of ductility and toughness. Thus, to achieve the required levels of hardness, the developments are now focusing on railway wheels composed by microalloyed steels that are defined as carbon-manganese steels containing a small amount (less than 0.5% by mass) of strong carbide-forming elements such as niobium (Nb), vanadium (V), molybdenum (Mo) and/or titanium. The MWL Brazil began in 2008, together with Unicamp, a research project on the development of railway wheel made of microalloyed steel and, later on 2012, EPUSP joined to the project reinforcing the importance of the project. During this work, project developed a disk-on-disk wear test machine that would attend the specifications of the standard AAR (Association of American Railroads). Besides, there was also an interest on further knowing the behavior of these steels, that is, it would be necessary to obtain the continuous cooling curves (CCC). In this work, the analysis of CCC showed that the addition of microalloying elements contributed in refining the austenitic grain size due to fine Nb and V carbides formation; delayed the formation of ferrite and pearlite, which reduced the interlamellar spacing of pearlite; and increased the hardenability of steels. However, the addition of microalloying did not change the starting martensite formation temperature, but increased the hardenability. It was also observed that the formation of martensite was not finished at room temperature and all studied steels presented retained austenite. The analysis of samples taken from the tread of railway wheels, with ferritic-pearlitic structure revealed that the vanadium steel showed the best results in all tests of strength (at room temperature and 540 °C), K1C and Charpy test if compared to steels without microalloying or with the addition of Nb+Mo. The superior performance vanadium steel was attributed to the smallest austenite grain size and the finest interlamellar spacing of the pearlite. In the wear test, the weight loss was greater in the niobium microalloyed steel. The developed prototype of the disk-on-disk wear test machine only provided reliable results up to 250,000 cycles; it not reached the minimum value specified by the AAR. However, the experience was essential to enhance a new prototype that is commissioning / Doutorado / Materiais e Processos de Fabricação / Doutora em Engenharia Mecânica

A modelagem matemática por meio de equações diferenciais é uma importante ferramenta para prever o comportamento de baterias redox de vanádio, pois ela pode contribuir para o aperfeiçoamento do produto e melhor entendimento dos princípios da sua operação. Os estudos de modelagem podem ser aliados à análise assintótica no intuito de promover reduções ou simplificações que tornem os modelos menos complexos, isso é feito a partir da observação da importância que cada termo exerce sobre as equações. Tais simplificações são úteis neste contexto, visto que os modelos geralmente abordam uma célula apenas - a menor unidade operacional da bateria - enquanto aplicações reais exigem o uso de dezenas ou centenas delas implicando em uma maximização do uso de recursos computacionais. Neste trabalho, foram investigadas múltiplas formas de reduções assintóticas que empregadas na construção dos modelos puderam acelerar o tempo de processamento em até 2,46 vezes ou reduzir os requisitos de memória principal em até 11,39%. As simulações computacionais foram executadas pelo software COMSOL Multiphysics v. 4.4, e também por scripts desenvolvidos em ambiente de programação MATLAB. A validação dos resultados foi feita comparando-os a dados experimentais presentes na literatura. Tal abordagem permitiu também validar as rotinas implementadas para a simulação dos modelos comparando suas soluções com aquelas providas pelo COMSOL. / Mathematical modelling using differential equations is an important tool to predict the behavior of vanadium redox batteries, since it may contribute to improve the device performance and lead to a better understanding of the principles of its operation. Modelling can be complemented by asymptotic analysis as a mean to promote reductions or simplifications that make models less complex. Such simplifications are useful in this context, whereas these models usually addresses one cell only the smallest operating unit while real applications demand tens or hundreds cells implying on larger computational requirements. In this research, several options for asymptotic reductions were investigated and, applied to different models, were able to speed up the processing time in 2.46× or reduce the memory requirements up to 11.39%. The computational simulations were executed by COMSOL Multiphysics v.4.4, also by in-house code developed in MATLAB. The validation of results was done by comparing it to experimental results available in literature. Additionally, correlating the results provided by COMSOL with the ones arising from the implemented sub-routines allowed to validate the developed algorithm.

abstract: This research focuses mainly on employing tunable materials to achieve dynamic radiative properties for spacecraft and building thermal management. A secondary objective is to investigate tunable materials for optical propulsion applications. The primary material investigated is vanadium dioxide (VO2), which is a thermochromic material with an insulator-to-metal phase transition. VO2 typically undergoes a dramatic shift in optical properties at T = 341 K, which can be reduced through a variety of techniques to a temperature more suitable for thermal control applications. A VO2-based Fabry-Perot variable emitter is designed, fabricated, characterized, and experimentally demonstrated. The designed emitter has high emissivity when the radiating surface temperature is above 345 K and low emissivity when the temperature is less than 341 K. A uniaxial transfer matrix method and Bruggeman effective medium theory are both introduced to model the anisotropic properties of the VO2 to facilitate the design of multilayer VO2-based devices. A new furnace oxidation process is developed for fabricating high quality VO2 and the resulting thin films undergo comprehensive material and optical characterizations. The corresponding measurement platform is developed to measure the temperature-dependent transmittance and reflectance of the fabricated Fabry-Perot samples. The variable heat rejection of the fabricated samples is demonstrated via bell jar and cryothermal vacuum calorimetry measurements. Thermal modeling of a spacecraft equipped with variable emittance radiators is also conducted to elucidate the requirements and the impact for thermochromic variable emittance technology. The potential of VO2 to be used as an optical force modulating device is also investigated for spacecraft micropropulsion. The preliminary design considers a Fabry-Perot cavity with an anti-reflection coating which switches between an absorptive “off” state (for insulating VO2) and a reflective “on” state (for metallic VO2), thereby modulating the incident solar radiation pressure. The visible and near-infrared optical properties of the fabricated vanadium dioxide are examined to determine if there is a sufficient optical property shift in those regimes for a tunable device. / Dissertation/Thesis / Doctoral Dissertation Aerospace Engineering 2020

No description available.

The investigated subject for this diploma thesis is getting know properties of the vanadium redox battery (VRB), especially electrolyte. Specialization is applied to the state of charge of this cell and its measurements using the optical methods. Upon different state of charge is changed oxidation number of vanadium and resultant color of the electrolyte. Using spectrofotometry method that characteristic property is undergone measurement. The basic thing was learning to handle a measurement system. The first practical measurement was executed on example foils. Upon measurement of vanadium cell there was obtained the values of absorbation, which they were used for determination of state of charge.